Cobaltiferous azo dyestuffs



United States Patent COBALTIFEROUS AZO DYEST UFF S Reinhard Neier,Basel, Switzerland, assignor, by mesne assignments, to Saul & Co.,Newark, N. J., as nominee of Fidelity Union Trust Company, executivetrustee under Sandoz Trust No Drawing. Application December 2, 1955Serial No. 550,790

Claims priority, application Switzerland December 15, 1954 6 Claims.(Cl. 260-145) The present invention relates to cobaltiferous azodyestuffs which are useful as dyestuifs for Wool, silk and syntheticpolyarnide fibers.

More particularly, the invention has especial relation to a group ofcobaltiferous azo dyestuifs which correspond to the general formulawherein v represents hydrogen or methyl, w represents hydrogen,chlorine, methyl or nitro, and R represents 3-methoxypropyl or2-hydroxypropyl,

wherein the N- v group is in the 1 or 2 position of the naphthalenenucleus and in ortho-position to the azo group, the -S0 -NHR group is inthe 4, 5 or 6 position of the naphthalene nucleus, and wherein A standsfor A, or for a radical different from A but of the same generalformula, or for the radical of a monoazo compound obtained by coupling adiazotized Z-aminol-hydroxybenzenesulfonic acid amide with 2-(3'chloro)-phenylaminonaphthalene, or for the radical of a monoazo compound of thegeneral formula Or-Z (II) wherein x represents hydroxy or methoxy,

y represents hydrogen, methyl or acetylamino,

z represents low-molecular alkyl or the radical of an aliphatic,cycloaliphatic, araliphatic, aromatic or heterocyclic primary orsecondary amine which may carry further non-ionogenic substituents,

R represents an alkyl radical containing not less than 6 and not morethan 18 carbon atoms, and

R represents an alkyl or aryl radical.

The new cobaltiferous azo dyestuffs possess outstanding 5 2,839,520 IcePatented June 17, 1958 O2N (III) the 2 mols being of identical monoazocompound or of dilferent monoazo compounds of Formula III,

wherein a! :elii v represents hydrogen or methyl,

w represents hydrogen, chlorine, methyl or nitro, and R representsB-methoxypropyl or 2-hydroxypropyl,

R2 BIO-4.

wherein x represents hydroxy or methoxy,

y represents hydrogen, methyl or acetylarnino,

z represents low-molecular alkyl or the radical of an aliphatic,cycloaliphatic, araliphatic, aromatic or heterocyclic primary orsecondary amine which may carry further non-ionogenic substituents,

R represents an alkyl radical containing not less than 6 and not morethan 18 carbon atoms, and

R represents an alkyl or aryl radical.

in such a way the resulting dyestuff contains to 1 mol of the monoazocompound approximately /2 gram atom of cobalt in complex combination.

The metallization of the mixtures of the monoazo compounds is carriedout preferably with cobaltous acetate, cobaltous formiate and cobaltoussulfate in aqueous suspension, in solution, or in an organic medium, forexample formamide, or in an aqueous organic medium, e. g. in theconcentrated aqueous solution of an alkaline metal salt of alow-molecular aliphatic monocarboxylic acid. In the latter caseinsoluble metal compounds may also be employed, for example cobalthydroxide and cobalt carbonate. Metallization in an aqueous causticalkaline medium, effected by the addition of the metal salts in thepresence of derivatives which are able to form, with cobalt, complexcompounds soluble in a caustic alkaline medium, e. g. tartaric acid,citric acid or lactic acid, is particularly advantageous. When thesymbol x in the monoazo compounds of general Formula II representsmethoxy, metallization must be conducted With simultaneous splitting offof the methoxy group.

Since the cobaltiferous azo dyestuffs obtained according to theinvention contain to 1 mol of the monoazo compound approximately /2 gramatom of cobalt in complex combination, it is advisable to carry outmetallization with a quantity of cobalt-yielding agent containing lessthan two but at least one atom of cobalt to two molecules of the monoazocompound. The dyestufis are usually precipitated from the nietallizingsolution by an addition of salt, then filtered off, washed if desired,and finally dried.

The new cobaltiferous azo dyestuffs are either symmetrical dyestuffs ormixtures of symmetrical and asymmetrical dyestufis in which theasymmetrical dyestuff forms the main constituent. The dyestufi mixturesobtained according to the invention are distinguished from the mixturesproduced by simple mixing of 1:2 complex compounds obtained bymetallization of the individual monazo compounds, by the brighter shadesof their dyeings. Furthermore, the dyestufi mixtures according to theinvention behave in exhaustion tests like homogeneous dyestuffs, whichis not the case with mixtures produced by mechanical means.

The following examples illustrate the invention without limiting itsscope. All parts and percentages specified therein are by weight;temperatures are in degrees centigrade.

EXAMPLE 1 22.2 parts of the monoazo compound obtained by couplingdiazotized Z-amino-l--hydroxy-5-nitrobenzene with1aminonaphthalene-4-sulfonic acid-(2'-hydroxy)- propylamide aredissolved in 600 parts of water with the aid of 4 parts of sodiumhydroxide. To the solution is added a mixture of 7.1 parts ofcrystallized cobaltous sulfate, 2.8 parts of sodium hydroxide and 63par-ts of a 3% aqueous solution of tartaric acid, and the mass boiled onthe reflux until such time as the metalfree monoazo compound is nolonger indicated. The cobaltiferous azo dyestufi thus formed isprecipiated from the metallizing solution by an addition of sodiumchloride, then filtered otf, dried and ground. It is a dark powder whichdyes wool, silk, leather and synthetic polyamide fibres in blue shadesand corresponds to formula OaN 'In Table 1 further cobaltiferous azodyestuffs are enumerated. They are characterized by the diazo and azocomponents used for the production of the monoazo compounds and by theshades of their (lyeings on wool.

Table 1 EX Shade of the No. Diazo component 'Azo component ggggg ggigcompound on wool 2.- Z-amiuonaphthalene-fisulfonic acid-(2-hygroxw-propyla- 2-amino-1-hydroxy-5- nitrobenzeue.

with 1-aminonaphthalenel-sulfonic acid- (2-hydroxy)- propylamide and11.3 parts of the monoazo compound obtained by coupling diazotizedZ-amino-l-hydroxybenzene-4-sulfonic acid amide with2-(3-chloro)-phenylaminonaphthalene are heated with 7.1 parts ofcrystallized cobaltous sulfate in 150 parts of formamide at until nofurther metal-free monoazo compound is indicated in the metallizingmass. The cobalt complex compound thus formed is precipitated from thesolution by an addition of 20 parts of sodium chloride in 200 parts ofwater, then filtered off. It is purified by dissolving in water with theaid of sodium hydroxide, reneWed precipitation from the solution bymeans of sodium chloride, and filtering off or" the precipitate. Whendried and ground the cobaltiterous azo dyestutris obtained as a darkpowder which dyes wool, silk, leather and synthetic polyamide fibres inblue shades.

It is a mixture of three cobaltiferous azo dyestuffs, the mainconstituent corresponding to the formula N=N I I I H- I Cl C0 the twoother possessing the formulae SOzNH--CHzCH(OH)OH OzN Greenish blue.

and

EXAMPLE 8 10.3 parts of the monoazo compound produced by couplingdiazotized 2 amino 1 hydroxybenzene-4- sulfonic acid amide with 1acetoacetylamino 2 ethylhexane and "11.1 parts of the monoazo compoundobtained by coupling diazotized 2 amino 1 hydroxy-S- nitrobenzene with 2aminonaphthalene 6 sulfonic acid (2' hydroxy) propylamide are dissolvedwith the aid of 4 parts of sodium hydroxide in 600 parts of water. Tothis solution is added a solution of 7.1 parts of crystallized cobaltoussulfate, 2.8 parts of sodium hydroxide and 63 parts of a 3% aqueoussolution of tartaric acid, and the mass boiled on the reflux until themetalfree monoazo compound is no longer indicated. The resulting cobaltcomplex compound is precipitated by an addition of sodium chloride, andsubsequently filtered off, dried and ground. The cobaltiferous azodyestufi is a dark powderwhich dyes wool, silk, leather and syntheticpolyamide fibres in green shades.

It is a mixture of three cobaltiferous azo dyestuffs, the mainconstituent corresponding to the formula the two other possessing theformulae and 10.3 parts of the monoazo compound obtained by cou plingdiazotized 2 amino 1 hydroxybenzene 4 sulfonic acid amide withl-acetoacetylamino-2-ethy1hexane and 11.1 parts of the monoazo compoundobtained by coupling diazotized 2 amino 1 hydroxy 5 nitrobenzene with 1aminonaphthalene 5 sulfonic acid- (2-hydroxy)-propylamide are heatedwith 7.1 parts of crystallized cobaltous sulfate in 150 parts offormamide at -100 until no further metal-free monoazo compound isindicated in the metallizing mass. The cobalt complex compound thusformed is precipitated from the metallizing mass by the addition of asolution of 20 parts of sodium chloride and. 200 parts of water, andthen filtered off. It is purified by dissolving in water with the aid ofsodium hydroxide and renewed precipitation from the solution by means ofsodium chloride, the

' precipitate then being filtered off. The dried and groundcobaltiferous azo dyestuif is a dark powder which dyes wool, silk,leather and synthetic polyamide fibres in green shades.

It is a mixture of three cobaltiferous azo dyestuffs,

Hr-C o 1 part of Glaubers salt and 02 part of the cobaltiferous azodyestufi obtained according to the procedure described in Example 7 aredissolved in 500 parts of water. parts of wool, previously wetted out,are entered into the dyebath at 30 and the bath raised to 100 in thecourse of minutes. The temperature of the bath is maintained at 100 for60 minutes; during the dyeing process 0.2 part of concentrated aceticacid are gradually added. On completion of dyeing the wool, dyed in ablue shade, is rinsed with water and dried.

Synthetic polyamide fibres are dyed in the same way; silk is dyed atsomewhat lower temperatures, e. g. at 95.

I claim:

1. Cobalt-containing azo dyestuffs and mixtures of cobalt-containing azodyestuffs which correspond to the general formula wherein v stands for amember selected from the group consisting of hydrogen and methyl, wstands for a member selected from the group consisting of hydrogen,chlorine, methyl and nitro, R stands for a member selected from thegroup consisting of 3'-methoxypropyl and 2'-hydroxypropyl, wherein theNW-v group is in one of the 1 and 2 positions of the napththalenenucleus and in ortho-position to the azo group, the -SO NH-R group is inone of the 4, 5 and 6 positions of the naphthalene nucleus, and whereinthe radical A stands for a member selected from the radical A, a radicaldifierent from A and having the same general formula, the radical of amonoazo compound obtained by coupling a diazotizedZ-amino-l-hydroxybenzenesulfonic acid amide with2-(3.'-chloro-phenylaminonaphthalene, and the radical of a monoazocompound of the general formula 3. A mixture of cobalt-containing azodyestuffs which correspond to the formulae I I N-H I H:

gs'mmg O zNH:

am and TEN-0:3 Eim-NEwmm-Hmm-cm NO 5 I I I N H H N 11- d/ 01 10 C 0 0 lI I 4. A mixture of cobalt-containing azo dyestufis which correspond tothe formulae 0 I H-N meomno-mc-nn-ms HPCHI SOa-NH-CHr-CHrCHz-OCE:

I NH [I H- lod I EN OaN 13:0 G-HgO-HgO-HzO-HN-O.

m0 m0 Jim-01s 40 H|C-H1C-( J-HN Ha Hx 0:!)

References Cited in the file of this patent FOREIGN PATENTS 1,085,262France July 21, 1954 1,092,850 France Nov. 10, 1954 and and

mo-wamc-mc-mw-o.

6. A mixtilre of cobalt-containing azo dyestufls which correspond to theformulae SOgNHF-CHa-CHr-CHr-OCEa

1. COBALT-CONTAINING AZO DYESTUFFS AND MIXTURES OF COBALT-CONTAINING AZODYESTUFFS WHICH CORRESPOND TO THE GENERAL FORMULA